US3987086A - Hindered hydroxyphenylalkanoates of substituted vicinal glycols - Google Patents

Hindered hydroxyphenylalkanoates of substituted vicinal glycols Download PDF

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US3987086A
US3987086A US05/532,126 US53212674A US3987086A US 3987086 A US3987086 A US 3987086A US 53212674 A US53212674 A US 53212674A US 3987086 A US3987086 A US 3987086A
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tert
butyl
esters
bis
methyl
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Martin Dexter
David Herbert Steinberg
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Novartis Corp
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Ciba Geigy Corp
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Priority to US05/532,126 priority Critical patent/US3987086A/en
Priority to NL7514024A priority patent/NL7514024A/xx
Priority to DE2555520A priority patent/DE2555520C2/de
Priority to FR7537924A priority patent/FR2294172A1/fr
Priority to BE162672A priority patent/BE836549A/xx
Priority to GB50783/75A priority patent/GB1529470A/en
Priority to JP50149042A priority patent/JPS6118592B2/ja
Priority to US05/693,386 priority patent/US4058502A/en
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Priority to JP60025073A priority patent/JPS615053A/ja
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/06—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/286—Esters of polymerised unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/084—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2221/043—Polyoxyalkylene ethers with a thioether group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/46—Textile oils

Definitions

  • esters of this invention are prepared by usual esterification procedures from a substituted vicinal glycol and an acid of formula ##SPC2##
  • the substituted vicinal glycols are prepared by reaction of glycidol with an alcohol or mercaptan in the presence of an alkaline catalyst.
  • the compounds are useful as stabilizers for organic materials, especially polyolefins, which degrade upon exposure to light and heat.
  • This invention pertains to substituted vacinal glycol esters of hindered hydroxyphenylalkanoic acids and to organic materials normally subject to oxidative, thermal and UV light degradation stabilized with said ester compounds.
  • the compounds of this invention are those having the formula ##STR1## wherein R 1 is alkyl of 1 to 30 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkylthioethyl of 4 to 27 atoms in the chain or alkylpolyoxyalkylene of 4 to 27 atoms in the chain,
  • Z is oxygen or sulfur
  • R 2 is the group ##SPC3##
  • R 3 is hydrogen, alkyl of 1 to 8 carbon atoms, cycloalkyl of 5 to 6 carbon atoms of ⁇ -methylbenzyl,
  • R 4 is alkyl of 1 to 8 carbon atoms or cycloalkyl of 5 to 6 carbon atoms
  • R 5 is hydrogen or lower alkyl of 1 to 4 carbon atoms, or R 3 and R 5 together are a butylene chain which, together with the phenyl ring, form a tetrahydronaphthyl group, and provided when R 3 is hydrogen, R 5 is alkyl and R 4 is located on the carbon atom ortho to the hydroxyl group, and
  • A is a covalent carbon bond or a straight or branched lower alkylene having 1 to 8 carbon atoms.
  • the R 1 group can be alkyl of 1 to 30 carbon atoms such as methyl, n-butyl, n-octyl, t-dodecyl, n-octadecyl, n-tetracosanyl or n-triacontanyl.
  • R 1 is alkyl of 1 to 18 carbon atoms, such as methyl, n-butyl, n-dodecyl or n-octadecyl.
  • the R 1 group can be cycloalkyl of 5 to 12 carbon atoms such as cyclopentyl, cycloheptyl, cyclohexyl, cyclooctyl or cyclododecyl.
  • R 1 is also alkylthioethyl of 4 to 27 atoms in the chain such as 2-methylthioethyl, 2-(n-octylthio)ethyl and 2-(tetracosanylthio)ethyl.
  • R 1 can also be alkylpolyoxyalkylene of 4 to 27 atoms in the chain having the general structure R°(OC n H 2n ) h or R° (OCH 2 CHR') h where R° is alkyl of 1 to 18 carbon atoms, n is 2 to 4, R' is hydrogen, methyl or ethyl and h is 1 to 3.
  • R 3 and R 4 groups can be straight or branched lower alkyl groups, having 1 to 8 carbon atoms as for example, methyl, ethyl, isopropyl, n-butyl, tert-butyl, tert-amyl or n-octyl.
  • R 3 and R 4 can also be cycloalkyl of 5 to 6 carbon atoms such as cyclopentyl or cyclohexyl.
  • R 3 can also be ⁇ -methylbenzyl.
  • R 3 is a straight or branched alkyl group of 1 to 4 carbon atoms, such as methyl, ethyl, isopropyl or tert-butyl. Most preferably R 3 is methyl or tert-butyl.
  • R 4 is a branched alkyl of 3 to 8 carbon atoms, such as isopropyl, sec-butyl, tert-butyl, sec-amyl, tert-amyl, sec-octyl or tert-octyl. Most preferably R 4 is tert-butyl.
  • R 5 is hydrogen or alkyl of 1 to 3 carbon atoms, such as methyl, ethyl or n-propyl. Most preferably R 5 is hydrogen or methyl.
  • A is a covalent carbon bond or a straight or branched lower alkylene of 1 to 8 carbon atoms such as methylene, ethylene, 2,3-propylene, trimethylene, 1,1-dimethylethylene, 1,1-butylidene, 2-methyl-1,1-propylidene or 1,1-octylidene.
  • A is a straight chain alkylene of 1 to 3 carbon atoms, that is, methylene ethylene or trimethylene. Most preferably A is methylene or ethylene.
  • esters of this invention are prepared by usual esterification procedures from the appropriate substituted vicinal glycol and an acid of the formula I ##SPC4##
  • the acid halide derivatives of the above cited acids are made in a conventional manner using standard halogenating agents such as thionyl chloride, phosphorus trichloride and phosphorus oxychloride.
  • the lower alkyl esters are conveniently made by an acid catalyzed reaction of the above-cited acid with a lower alcohol, such as methanol.
  • A is ethylene or substituted ethylene
  • the lower alkyl esters are conveniently made by reaction of a substituted phenol (II) with an acrylate ester as represented below. ##SPC5##
  • R 6 is hydrogen or lower alkyl of 1 to 6 carbon atoms and R is alkyl of 1 to 4 carbon atoms. Processes of this type are disclosed for example in U.S. Pat. No. 3,247,240 (Apr. 9, 1966) and U.S. Pat. No. 3,364,250 (Jan. 16, 1968).
  • ester intermediates may also be made by reacting a substituted phenol with an acrylonitrile as represented below. ##SPC6##
  • R 7 and R 8 are lower alkyl of 1 to 8 carbon atoms or together form a morpholine or piperidine ring with the nitrogen atom.
  • R 7 and R 8 are methyl.
  • Acids of formula I can also be prepared by reaction of substituted phenolate anions with appropriate halogenoalkane carboxylate esters, amides or nitriles where A may be straight or branched alkylene of 2 to 8 carbon atoms.
  • di- and trialkylated phenols (II) contemplated for use as starting materials to make the compounds of this invention are known compounds which are available commercially.
  • the preparation of 2,6-diisopropyl-3-methylphenol and 2,6-di-tert-butyl-3-methylphenol is disclosed in Japanese patent application 7015,491.
  • the preparation of 2,3-dimethyl-6-tert-butylphenol is disclosed by G. Parc, Revue de L'Institut Francais du Petrole, XV, 693 (1960).
  • substituted phenols may be made by the selected alkylation of phenolic starting materials using acid catalysis such as p-toluene sulfonic acid and selected olefins such as propylene, isobutylene and 2,4,4-trimethylpentene-1.
  • acid catalysis such as p-toluene sulfonic acid and selected olefins such as propylene, isobutylene and 2,4,4-trimethylpentene-1.
  • R 4 may be either ortho to the hydroxyl group or the A group, preferably R 4 is ortho to the hydroxyl in esters of this invention.
  • the key substituted vicinal glycol intermediates required to prepare the esters of this invention where Z is oxygen are conveniently made by the following sequence of reactions which involve preparation of an allyl ether followed by subsequent oxidation of the allyl moiety to a vicinal glycol by way of the corresponding oxirane.
  • X is halogen
  • M + is a cation such as lithium, sodium, potassium or ammonium
  • solvent may be optional and the oxidizing agent is a peracid such as peracetic acid.
  • substituted vicinal glycols are useful as chemical intermediates in the preparation of stabilizers of this invention and a myriad of other products such as synergists, extreme pressure additives for lubricants, pesticides, fuel additives and the like.
  • Esters of 3,5-dialkyl-4-hydroxyphenylalkanoic acids and alkane polyols are described in U.S. Pat. No. 3,644,482. Many of these compounds are crystalline or vitreous solids which are highly effective stabilizers against thermo-oxidative aging, i.e. they are solid antioxidants. Moreover they generally have only limited solubility in those solvents employed technically in large amounts such as aliphatic hydrocarbons.
  • esters of 3,5-dialkyl-4-hydroxyphenylalkanoic acids and mixtures of at least two non-identical alkanediols are described in U.S. Pat. No. 3,779,945. These mixed esters do provide very suitable stabilization for organic materials subject to degradation, and in addition are liquids which can be pumped, proportioned and fed and which are quite soluble in organic solvents permitting their use in highly concentrated solutions.
  • esters of this invention are also liquids which exhibit all the processing, solubility and utility advantages shown by the mixed esters described in U.S. Pat. No. 3,779,945.
  • the substrates of particular importance are olefin polymers such as polyethylene, polypropylene, olefin copolymers and blends thereof.
  • Polypropylene is especially well stabilized with the compounds of this invention.
  • the stabilizers of this invention are particularly useful in protecting polymer compositions subjected to high temperature processing as well as end uses involving elevated temperatures.
  • the esters of this invention exhibit good stabilization activity in polypropylene even in the absence of a thio ester co-stabilizer such as distearyl ⁇ -thiodipropionate (DSTDP).
  • DSTDP distearyl ⁇ -thiodipropionate
  • the stabilization protection afforded polypropylene by the esters of this invention is surprisingly high, for exceeding in most cases that provided in similar formulations by commercial stabilizers of choice described in U.S. Pat. No. 3,285,855 or by liquid mixed ester stabilizers described in U.S. Pat. No. 3,779,945.
  • esters of the present invention exhibit this superior degree of stabilization even though the molar concentration of the active hindered phenol moiety from the ester stabilizer of this invention in polypropylene is much less than the molar concentration of hindered phenol moiety in polypropylene when commercial stabilizers of choice are used. That superior stabilization can be afforded with a significant lower amount of the relatively expensive hindered phenol moiety is of great economic importance.
  • the less additive required in a polymer composition usually benefits retention of its basic physical properties.
  • esters of this invention While the liquid physical nature of these esters may well facilitate their introduction and compatibilization in the amorphous areas of the polypropylene system where stabilization activity is most needed, it is postulated that the molecular structure of the esters is significantly different from the prior art stabilizers and that this difference in structure may well account for the great effectiveness of the esters of this invention.
  • esters are all derived from substituted vicinal 2,3-propanediols having preferably either a long alkyloxy or alkylthio group substituted on the 1-position carbon.
  • the esters of this invention have one solubilizing hydrocarbon group attached to a carbon atom with one hindered phenol moiety on each of the two adjacent carbon atoms affording a particular spacial concentration of active groups which leads to a very efficient stabilization of polypropylene.
  • the prior art stabilizers are of four general types all differing significantly from the instant esters.
  • Type 1 a plurality of hindered phenol moieties surround a small hydrocarbon linking group. These materials are generally solids and relatively high melting materials with concomitant limited solubility in aliphatic hydrocarbon solvents.
  • One member of this group 1,1,1-butanetriyl tris[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Example 7, U.S. Pat. No.
  • Type 2 the hindered phenol moiety is joined by a single long hydrocarbon chain sometimes containing a heteroatom such as sulfur. (See U.S. Pat. No. 3,330,859, 3,441,575).
  • these types of stabilizers may be represented below where + represents a hindered phenolic moiety, and -- a short linking chain or pendant group and a long solubilizing hydrocarbon chain which may include a heteroatom such as oxygen or sulfur therein.
  • ester compounds of the present invention provide excellent stabilization protection not only for polymeric substrates such as polyolefins, polyacetals, polyesters and polyamides, but also for non-polymeric substances such as oils which undergo thermal and actinic degradation.
  • the stabilizer additive be a solid, preferably white, somewhat high melting material. This is especially true for polymeric substrates where small amounts of the additive are to be isolated then weighed accurately and added discretely into the polymeric system to be stabilized.
  • the compounds of the instant invention provide an equally beneficial physical form for such stabilizers are essentially colorless, high boiling liquids. These materials are stable, possess the requisite structures for enhancing solubility and compatibility in the substrates to be stabilized and provide by their totally liquid nature, as contrasted to a high-melting solid or a low-melting semi-solid, a particularly convenient method of addition to the substrate systems.
  • the compounds of this invention can be accurately metered and monitored into the substrate systems to be stabilized using standard liquid pumping devices.
  • esters of the invention are expected to find particular utility in stabilizing liquid substrates such as oils and in stabilizing polymeric substrates where liquid pumping devices can be expeditiously employed in adding the stabilizers during polymer processing.
  • the hindered hydroxyphenyl alkanoates of this invention are stabilizers of organic material normally subject to thermal and oxidative deterioration.
  • Materials which are thus stabilized include synthetic organic polymeric substances such as poly- ⁇ -olefins, polyethylene, polypropylene, cross-linked polyethylene, polybutylene including copolymers of ⁇ -olefins such as ethylene/propylene copolymer; dienes such as polybutadiene, polyisoprene, and the like, including copolymers with other monomers; polyurethanes and polyamides such as polyhexamethylene adipamide and polycaprolactam; polyesters such as polyethylene terephthalates; polycarbonates; polyacetals; unsaturated polyesters; polystyrene, polyethylene oxide; and copolymers such as those of high impact polystyrene containing copolymers of butadiene and styrene and those formed by the copolymerization of acrylonitrile
  • lubricating oil of the aliphatic ester type i.e., di(2-ethylene) azelate and other synthetic ester lubricants, pentaerythritol tetracaproate, and the like
  • spinning lubricants of the polyester type animal and vegetable derived oils, e.g., linseed oil, fat, tallow, lard, peanut oil, cod liver oil, castor oil, palm oil, corn oil, cottonseed oil, and the like; hydrocarbon materials such as gasoline, mineral oil, fuel oil, drying oil, mineral lube oils, cutting fluids, waxes, resins and the like, salts of fatty acids such as soaps and the like; and alkylene glycols, e.g., ⁇ -methoxyethylene glycol, methoxytriethylene glycol, triethylene glycol, octaethylene glycol, dibutylene glycol, dipropylene glycol and the like.
  • the substrates of particular importance are olefin polymers such as polyethylene, polypropylene, polybutylene and ethylene/vinyl acetate.
  • Polypropylene is especially well stabilized with the compounds of this invention.
  • the stabilizers of this invention are employed from about 0.01 to about 5% by weight of the stabilized composition, although this will vary with the particular substrate and application.
  • An advantageous range is from about 0.05 to about 2% and especially from about 0.1 to about 1%.
  • the stabilizers can be blended before polymerization or after polymerization, during the usual processing operations, for example, by dry blending, extruder compounding and hot-milling.
  • the composition then can be extruded, pressed, injected molded or otherwise fabricated into films, fibers, filaments, molded items and the like.
  • the heat stabilizing properties of these compounds advantageously stabilize the polymer against degradation during such processing at the high temperature generally encountered.
  • the useful life of polymeric materials is also extended by these stabilizers far beyond their ability to survive processing.
  • the stabilizers can also be dissolved in suitable solvents and sprayed on the surface of films, fabrics, filaments or the like to provide effective stabilization.
  • These compounds can also be used in combination with other additives such as sulfur-containing esters, e.g., distearyl ⁇ -thiodipropionate (DSTDP) in an amount of from 0.01 to 2% by weight of the organic material, and the like, pourpoint depressants, corrosion and rust inhibitors, dispersing agents, emulsifiers, antifoaming agents, carbon black, accelerators and other chemicals used in rubber compounding, plasticizers, color stabilizers, antistatic agents, antislip agents, antiblock agents, surface active agents, fillers, organophosphites, organothiophosphites, heat stabilizers, ultraviolet light stabilizers, antiozonants, dyes, pigments, metal deactivators, metal chelating agents, dyesites and the like.
  • DSTDP distearyl ⁇ -thiodipropionate
  • pourpoint depressants e.g., distearyl ⁇ -thiodipropionate (DSTDP) in an amount of from 0.
  • the following formula represents co-stabilizers which are in certain instances very useful in combination with the stabilizers of this invention: ##STR4## wherein R is an alkyl group having from 6 to 24 carbon atoms; and n is an integer from 1 to 6. Especially useful compounds of this type are dilauryl ⁇ -thiodipropionate and distearyl ⁇ -thiodipropionate.
  • the above co-stabilizers are used in the amount of from 0.01 to 2% by weight of the organic material, and preferably from 0.1 to 1%.
  • the light stabilizers are used in the amount of from 0.01 to 5% by weight of the organic material, and preferably from 0.1 to 1%. Illustrative examples of light stabilizers are listed below.
  • UV-Absorbers and light protection agents UV-Absorbers and light protection agents
  • 2-(2'-hydroxyphenyl)-2H-benztriazoles such as, for example, the 5'-methyl-, 3',5'-di-tert.-butyl-, 5'-tert.-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-, 5-chloro -3', 5'-di-tert.-butyl-, 5-chloro-3'-tert.-butyl-5'-methyl-, 3'-sec.-butyl-5'-tert.-butyl-, 3'- ⁇ -methyl-benzyl ⁇ -5'methyl-, 3'- ⁇ -methylbenzyl ⁇ -5'-methyl-5-chloro-, 4'-hydroxy-, 4'-methoxy-, 4'-octoxy-, 3',5'-di-tert.-amyl-, 3'-methyl-5'-carbomethoxyethyl-5-chloro-3',5'-di-tert.
  • 2,4-bis-(2'-hydroxyphenyl)-6-alkyl-s-triazines such as, for example, the 6-ethyl-, 6-undecyl- or 6-heptadecyl- derivatives.
  • 2-hydroxybenzophenones such as, for example, the 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy, 4-dodecyloxy-, 4-benzyloxy-, 4,2',4'-trihydroxy- or 2'-hydroxy-4,4'-dimethoxy- derivatives.
  • 1,3-bis-(2'-hydroxybenzoyl)benzenes such as, for example, 1,3-bis-(2'-hydroxy-4'hexyloxybenzoyl)benzene, 1,3-bis-(2'hydroxy-4'-octoxybenzoyl)benzene and 1,3-bis-(2'-hydroxy-4'-dodecyloxybenzoyl)benzene.
  • Esters of optionally substituted benzoic acids such as, for example, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4-tert.-butylbenzoyl)resorcinol, benzoylresorcinol, 3,5-di-tert.- butyl-4-hydroxybenzoic acid 2,4-di-tert.-butylphenyl ester, octadecyl ester or 2-methyl-4,6-di-tert.-butylphenyl ester, and the alkyl esters of 4-(3,5-di-tert-butyl-4-hydroxybenzoyloxy)-3,5-di-tert-butylbenzoic acid.
  • benzoylresorcinol 3,5-di-tert.- butyl-4-hydroxybenzoic acid 2,4-di-tert.-butylphenyl ester, o
  • Acrylates such as, for example, ⁇ -cyano- ⁇ , ⁇ -diphenylacrylic acid ethyl ester or isooctyl ester, ⁇ -carbomethoxycinnamic acid methyl ester, ⁇ -cyano- ⁇ -methyl-p-methoxycinnamic acid methyl ester or butyl ester and N-( ⁇ -carbomethoxy-vinyl)-2-methylindoline.
  • Nickel compounds such as, for example, nickel complexes of 2,2'-thio-bis-4-(1,1,3,3-tetramethylbutyl)phenol, such as the 1:1 and 1:2 complex, optionally with other ligands such as n-butyl-, triethanol-, cyclohexyl- or N-cyclohexyldiethanolamine; nickel complexes of bis- ⁇ 2-hydroxy-4(1,1,3,3-tetramethylbutyl)phenyl ⁇ sulfone, such as the 2:1 complex, optionally with other ligands such as 2-ethylcaproic acid; nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert.-butylbenzylphosphonic acid monoalkyl esters, such as the methyl, ethyl or butyl ester, the nickel complex of (2-hydroxy-4-methylphenyl)undecylketonoxime and nickel 3,5-di-tert.-butyl-4-
  • Oxalic acid diamides such as, for example, 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert.-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis-(3-dimethylaminopropyl)oxalamide, mixtures of o- and p-methoxy and o- and p-ethoxy-di-substituted oxanilides and mixtures of 2-ethoxy-5-tert.-butyl-2'-ethyloxanilide with 2-ethoxy-2'-ethyl-5,4'-di-tert.-butyloxanilide.
  • Sterically hindered amines such as, for example 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy 2,2,6,6-tetramethylpiperidine, bis-(2,2,6,6-tetramethylpiperidyl) sebacate and 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5] decan-2,4-dione.
  • reaction mixture became a clear orange solution immediately and was heated at reflux for another 2 hours.
  • the reaction mixture was then cooled to room temperature and neutralized with glacial acetic acid. After removing the precipitated sodium acetate and stripping off the toluene solvent, the desired product was obtained as the residue in a crude yield of 68 grams (quantitative yield).
  • the 1-n-octadecyloxy-2,3-propanediol could be further purified by vacuum distillation to give a 18% yield of pure material boiling at 215°-220° C/0.25mm.
  • Unstabilized polypropylene powder (Hercules Profax 6501) was thoroughly blended with 0.2% by weight of the indicated stabilizer compound. Also prepared were samples of polypropylene containing 0.1% by weight of the same stabilizer and 0.3% by weight of distearyl ⁇ -thiodipropionate (DSTDP). The blended materials were then milled on a two-roll mill at 182° C for 10 minutes after which time the stabilized polypropylene was sheeted from the mill and allowed to cool.
  • DSTDP distearyl ⁇ -thiodipropionate
  • the milled polypropylene sheets were then cut into pieces and pressed for 7 minutes on a hydraulic press at 218° C and 275 psi (19.25 Kg/cm 2 ) pressure.
  • the resulting plaques of 25 mil (0.635 mm) thickness were tested for resistance to accelerated aging in a forced draft oven at 150° C. When the plaques showed the first signs of decomposition (eg. cracking or brown edges) they were considered to have failed.
  • the results are shown in Table I below.
  • esters of this invention are very effective in the absence of a thio ester co-stabilizer, they exhibit outstanding effectiveness in the presence of such co-stabilizers.
  • esters of this invention at the 0.2% by weight concentration are more effective in most cases than the comparative esters listed above and tested at the 0.5% concentration level and in all cases based on molar concentration of the hindered phenol moiety as seen in Example 6.
  • Test specimens were prepared exactly as described in Example 6 except that the stabilized polypropylene contained 0.2% by weight of the various esters of this invention and 0.5% by weight of 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chloro-2H-benzotriazole as a co-stabilizer. Results of accelerated aging tests in a forced draft oven at 150° C are shown in Table II below
  • Test specimens were prepared exactly as those described in Example 6 except that the milled polypropylene sheets were cut into pieces and pressed for 3 minutes on a hydraulic press at 218° C and 275 psi (19.25 Kg/cm 2 ) pressure.
  • the resulting sheet of 5 mil (0.127 mm) thickness was tested in a fluorescent sunlight black light environment with the development of carbonyl absorption in the infrared spectrum at the 585 millimicron wavelength being the measure of stabilization protection afforded by the stabilizers present in the polypropylene. Failure was taken as the hours required to cause the carbonyl absorption to reach a value of 0.5. Such a value correlates with the reduction of physical properties of the polypropylene pellicle to unacceptable levels.
  • Table III The results are set out in Table III.
  • Pellets 500 g of unstabilized nylon-6,6 (Zytel 101, DuPont) are placed in a Kitchen Aid Mixer. With mixing a solution of 0.5% (based on the weight of nylon) of 1-cyclohexylthio-2,3-bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamoyloxy)propane in 20 ml of methylene chloride is added slowly. Sodium hypophosphite (0.5 gm 0.14) is dissolved in 20 ml of water and added slowly with mixing to the nylon pellets after the antioxidant solution has been added and most of the methylene chloride has evaporated. The stabilized pellets are dried at 80° C at ⁇ 1 mm Hg. for 4 hours.
  • the polyamide formulation is extruded at 600° F (315.6° C) through at 1/4 inch (0.635 cm) die into a rod which is water cooled and chopped into pellets.
  • the pellets are dried at 80° C at ⁇ 1 mm for 4 hours.
  • the dried pellets are compression molded into 5 mil (0.127 mm) thick film by pressing at 290° C for 4 minutes at 6000 psi (57.75 Kg/cm 2 ).
  • the films are oven aged at 150° C in a forced draft oven and samples are removed periodically.
  • the specific viscosity of the samples are determined using a 1% formic acid solution at 25° C.
  • the sample stabilized with the above noted stabilizer required longer aging time to reduce its viscosity by one-half than the unstabilized sample.
  • Unstabilized high impact polystyrene resin is dry blended with 0.01% by weight of the resin of 1-n-octadecyloxy-2,3-bis(3,5-di-tert-amyl-4-hydroxyhydrocinnamoyloxy)propane.
  • the sheets are then cut into plaques of 2 inch ⁇ 2 inch (5.08 cm ⁇ 5.08 cm.).
  • the plaques are then oven aged at 80° C and color measurements made periodically using a Hunter Color Difference Meter Model D25.
  • the polystyrene samples stabilized with the above stabilizer develops the undesirable yellow discoloration substantially later than the time that such discoloration occurred in the unstabilized samples.
  • Unstabilized linear polyethylene (HiFax 4401) is solvent blended in methylene chloride with 0.2 by weight of the substrate of 1-n-hexadecylthio-2,3-bis(2,3-dimethyl-5-tert-butyl-4-hydroxyhydrocinnamoyloxy)propane and then vacuum dried. The resin is then extruded at 450° F (232.2° C) using a 3/4 inch (1.905 cm) extruder having a 24:1 L/D ratio. The melt flow rate of a sample of the resin is determined after each extrusion according to ASTM test D-1238. Polyethylene stabilized with above compound is found to undergo less change in the melt flow rate than the unstabilized polyethylene.
  • a quantity of SBR emulsion containing 100 g of rubber (500 ml of a 20% SBR emulsion obtained commercially from Texas U.S. as Synpol 1500) previously stored under nitrogen, is placed in a beaker and stirred vigorously. The pH of the emulsion is adjusted to 10.5 with a 0.5N NaOH solution.
  • the coagulated rubber is isolated by filtration through cheese cloth, and rinsed with distilled water. After three subsequent washings with fresh distilled water, the coagulated rubber is dried, first at 25 mm Hg and finally to constant weight under high vacuum ( ⁇ 1 mm) at 40° to 45° C.
  • the dried rubber (25 g) is heated under nitrogen at 125° C in a Brabender mixer and to this is added with mixing 0.1% by weight of 1-n-dodecylthio-2,3-bis(3,5-dioctyl-4-hydroxyhydrocinnamoyloxy)propane.
  • Portions of the rubber are oven aged at 100° C. At various intervals gel content is determined on the rubber. The rubber stabilized with the above compound shows much less gel formation than the unstabilized sample.
  • the stabilized sheets are then remolded for 2 minutes at contact pressure and for 3 minutes at 300 psi (21 Kg/cm 2 ) at 215° C to give plaques 1.5 ⁇ 1.5 inch ⁇ 125 mil (3.81 cm ⁇ 5.715 cm ⁇ 3.175 mm.).
  • the plaques are aged in the oven at 60° C and the weight loss of the specimen is determined periodically until a 4% weight loss is reached.
  • the stabilized sample takes a much longer time to reach this 4% weight loss than does the unstabilized sample.
  • Unstabilized, thoroughly dried polyethylene terephthalate chips are dry blended with 1.0% by weight of 1-n-decyloxy-2,3-bis(2,3-dimethyl-4-hydroxyphenylacetoxy)propane.
  • 60/10 denier multifilament is melt spun at a melt temperature of 290° C and cold oriented 3 to 1.
  • the oriented fibers are wound into skeins and oven aged at 140° C.
  • the stabilized material exhibits greater retention of tensile strength after 24 hours than the stabilized material.
  • a stabilized high temperature lubricating oil is prepared by incorporating 0.05% by weight of 1-n-octadecylthio-2,3-bis(3,5-di-tert-butyl-4-hydroxyphenylacetoxy)propane to the lubricant which comprises diisoamyl adipate.
  • the stabilized composition is compared with the unstabilized lubricant by heating at 175° C in the presence of air and metallic catalysts according to the test method described in Military Specification Mil-I-7808c. After 72 hours, the blank containing no stabilizer contains more sludge and has a greater viscosity than the stabilized lubricant.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
US05/532,126 1974-12-12 1974-12-12 Hindered hydroxyphenylalkanoates of substituted vicinal glycols Expired - Lifetime US3987086A (en)

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Application Number Priority Date Filing Date Title
US05/532,126 US3987086A (en) 1974-12-12 1974-12-12 Hindered hydroxyphenylalkanoates of substituted vicinal glycols
NL7514024A NL7514024A (nl) 1974-12-12 1975-12-02 Gehinderde hydroxyfenylalkanoaten van propanolen en gestabiliseerde preparaten.
DE2555520A DE2555520C2 (de) 1974-12-12 1975-12-10 Sterisch gehinderte, phenolische Hydroxylgruppen enthaltende Carbonsäurepropylester und stabilisierte Kompositionen
BE162672A BE836549A (fr) 1974-12-12 1975-12-11 Esters de propanols et d'hydroxyphenyl-alcanoiques utilisables pour stabiliser des matieres organiques
FR7537924A FR2294172A1 (fr) 1974-12-12 1975-12-11 Esters de propanols et d'hydroxyphenyl-alcanoiques utilisables pour stabiliser des matieres organiques
GB50783/75A GB1529470A (en) 1974-12-12 1975-12-11 Hindered hydroxyphenylalkanoates of propanols and stabilized compositions
JP50149042A JPS6118592B2 (enrdf_load_stackoverflow) 1974-12-12 1975-12-12
US05/693,386 US4058502A (en) 1974-12-12 1976-06-07 Stabilized compositions containing hindered hydroxyalkanoates
JP60025073A JPS615053A (ja) 1974-12-12 1985-02-12 安定化有機物質の製造方法

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049751A (en) * 1976-04-26 1977-09-20 Dart Industries Inc. Extraction resistant polyolefin stabilizers
US4171298A (en) * 1976-11-01 1979-10-16 Argus Chemical Corporation Phenolic ester synthetic resin stabilizers
US5068433A (en) * 1984-08-02 1991-11-26 Farmitalia Carlo Erba, S.R.L. Process for preparation of 3-substituted derivatives of 1-amino-2-hydroxy propane
US5618778A (en) * 1984-06-29 1997-04-08 Ciba-Geigy Corporation Additives for lubricants

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU288839A (en) * 1939-06-27 1940-05-23 Thegeneral Electric Company Limited Improvements in optical projection apparatus
FR1337163A (fr) * 1961-10-30 1963-09-06 Geigy Ag J R Stabilisation de matières organiques au moyen d'esters contenant un groupe alkylhydroxyphényle
FR1436393A (fr) * 1964-06-02 1966-04-22 Geigy Ag J R Procédé de préparation d'esters
US3285855A (en) * 1965-03-11 1966-11-15 Geigy Chem Corp Stabilization of organic material with esters containing an alkylhydroxy-phenyl group
US3441575A (en) * 1961-10-30 1969-04-29 Geigy Chem Corp Esters of di(lower)alkylhydroxyphenyl alkanoic acid containing a hetro atom

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU288839A (en) * 1939-06-27 1940-05-23 Thegeneral Electric Company Limited Improvements in optical projection apparatus
FR1337163A (fr) * 1961-10-30 1963-09-06 Geigy Ag J R Stabilisation de matières organiques au moyen d'esters contenant un groupe alkylhydroxyphényle
US3441575A (en) * 1961-10-30 1969-04-29 Geigy Chem Corp Esters of di(lower)alkylhydroxyphenyl alkanoic acid containing a hetro atom
FR1436393A (fr) * 1964-06-02 1966-04-22 Geigy Ag J R Procédé de préparation d'esters
US3285855A (en) * 1965-03-11 1966-11-15 Geigy Chem Corp Stabilization of organic material with esters containing an alkylhydroxy-phenyl group

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049751A (en) * 1976-04-26 1977-09-20 Dart Industries Inc. Extraction resistant polyolefin stabilizers
US4171298A (en) * 1976-11-01 1979-10-16 Argus Chemical Corporation Phenolic ester synthetic resin stabilizers
US5618778A (en) * 1984-06-29 1997-04-08 Ciba-Geigy Corporation Additives for lubricants
US5892051A (en) * 1984-06-29 1999-04-06 Ciba Specialty Chemicals Corporation Additives for lubricants
US5068433A (en) * 1984-08-02 1991-11-26 Farmitalia Carlo Erba, S.R.L. Process for preparation of 3-substituted derivatives of 1-amino-2-hydroxy propane
US5391735A (en) * 1984-08-02 1995-02-21 Farmitalia Carlo Erba S.P.A. Process for the preparation of 3-substituted derivatives of 1-amino-2-hydroxy-propane

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JPS6119616B2 (enrdf_load_stackoverflow) 1986-05-17
JPS615053A (ja) 1986-01-10

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